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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Self-Assembly of a Triblock Copolymer in the Presence of a Rigid Conjugated Polyelectrolyte

The properties of conducting polymers are strongly influenced by structural changes induced by long-range order, which can be achieved by using block copolymers that self-assemble into crystalline structures. These blends result in unique mesophases distinct from the pure components with self-assembly behavior modulated by solution conditions and polymer architectures. High-throughput small-angle X-ray scattering data of aqueous Pluronic P123 (PEO 20 –PPO 70 –PEO 20 ) and conjugated polyelectrolyte poly[3-(potassium-4-butanoate) thiophene-2,5-diyl] (PPBT) blends at various concentrations and temperatures were automatically classified into phase maps by autophasemap, an unsupervised statistical analysis algorithm. The outlined phase boundaries revealed that adding PPBT to high P123 concentrations induced a transition from cubicly ordered spherical micelles to hexagonally packed cylindrical micelles. Shear alignment via rheological small-angle neutron scattering of the blends produced monolithic oriented cubic and hexagonal crystal gels. Furthermore, these insights into the self-assembly of conductive polymer blends will aid in the design of soft materials with tunable structural and electronic properties.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Adverse Effect of Polyelectrolyte Complexation on the CO 2 Permeability of Polyvinylamine Copolymers

Polyvinylamine (PVAm) is one of the most studied polymers for facilitated transport membranes (FTMs) in CO 2 separation applications. In this study, poly(N-vinylformamide) (PNVf) was hydrolyzed to prepare a range of PNVf-PVAm copolymer compositions and the effect of PVAm fraction on CO 2 permeability and CO 2 /N 2 selectivity these polymers examined. The most permeable film was the polymer containing 52 mol% PVAm units with a CO 2 permeability of 353 Barrer and CO 2 /N 2 selectivity of 96, when tested at 60°C with humidified 14/86 CO 2 /N 2 mixed gas. Despite containing a higher loading of amines to act as CO 2 carriers, higher PVAm contents yielded significantly lower CO 2 permeability, without a loss of selectivity. This trend was not due to polymer crystallization since none of the PVAm films exhibited crystallinity in X-ray diffraction analysis. The loss of gas permeability at high PVAm content was instead due to strong polyelectrolyte interactions between polymer chains formed when PVAm reacts with CO 2 . Since only the PVAm units are ionized upon reaction with CO 2 , with the PNVf units remaining neutral, the density of these ionic effects increased as PVAm content increased, leading to increased resistance to gas permeation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

3D Printing of Polyelectrolyte Complex-Integrated Photocurable Hydrogel Resins

In this study, we developed a photocurable hydrogel resin incorporating a polyelectrolyte complex (PEC) for 3D printing. Acrylamide-based monomers were formulated with varying PEC contents (0–15 wt %) in an aqueous KBr medium to fabricate patterned porous hydrogel structures. The morphology of printed hydrogels was characterized by field-emission scanning electron microscopy and energy-dispersive X-ray spectroscopy. Notably, the PEC5 and PEC10 formulations exhibited optimal thermal stability and compressive properties, attributed to the homogeneous distribution of PEC domains within the hydrogel matrix. Furthermore, dye adsorption experiments demonstrated excellent removal efficiency, highlighting the potential of PEC-containing hydrogels for environmental remediation applications, particularly in the treatment of dye-contaminated wastewater.

Yang, Jinchul [University of Tennesse Knoxville]↗
DOE OSTI2020

Crossover from Rouse to Reptation Dynamics in Salt-Free Polyelectrolyte Complex Coacervates

Considerable interest in the dynamics and rheology of polyelectrolyte complex coacervates has been motivated by their industrial application as viscosity modifiers. A central question is the extent to which classical Rouse and reptation models can be applied to systems where electrostatic interactions play a critical role on the thermodynamics. By relying on molecular simulations, we present a direct analysis of the crossover from Rouse to reptation dynamics in salt-free complex coacervates as a function of chain length. This crossover shifts to shorter chain lengths as electrostatic interactions become stronger, which corresponds to the formation of denser coacervates. To distinguish the roles of Coulomb interactions and density, here we compare the dynamics of coacervates to those of neutral, semidilute solutions at the same density. Both systems exhibit a universal dynamical behavior in the connectivity-dominated (subdiffusion and normal diffusion) regimes, but the monomer relaxation time in coacervates is much longer and increases with increasing Bjerrum length. This is similar to the cage effect observed in glass-forming polymers, but the local dynamical slowdown is caused here by strong Coulomb attractions (ion pairing) between oppositely charged monomers. Our findings provide a microscopic framework for the quantitative understanding of coacervate dynamics and rheology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Origins of Enhanced Ion Transport in Nanostructured Anion-Conducting Polyelectrolytes

Ion-conducting polymer chemistry and microstructure profoundly impact membrane water uptake and ionic conductivity. Water uptake strongly impacts ionic conductivity; yet excess water uptake compromises ion-exchange membrane mechanical properties. Although nanophase separation has been proposed to overcome this trade-off, it is unclear how polymer backbone architecture governs ionic nanostructure and its subsequent impact on water uptake and conductivity. Here, we integrate experiments and molecular dynamics simulations to elucidate the role of backbone chemistry in governing ionic nanostructure, hydration behavior, and ion transport in anion-conducting polyelectrolytes (ACPs). We systematically investigate hydrocarbon polynorbornene (PNB)-based ACPs with three distinct backbone architectures: vinyl-addition polymerization (VAP), ring-opening metathesis polymerization (ROMP), and hydrogenated ROMP. While maintaining comparable ion exchange capacities (IECs) and identical side-chain chemistry, we isolate the effects of backbone structure. We show that nanophase-separated ionic nanostructures originate in the dry state and evolve upon hydration through heterogeneous water uptake, with water preferentially partitioning into ion-rich domains. This nanophase separation arises from a delicate interplay between ionic segregation propensity and the entropic barrier imposed by backbone stiffness. Specifically, flexible backbones intensify attractive ion–ion interactions by reducing the entropic penalty for backbone deformation, promoting nanophase separation, while rigid backbones suppress ionic nanostructure formation. Nanophase-separated ion domains locally concentrate water upon hydration, which in turn enables the connectivity required for fast transport at lower water concentration values. Furthermore, these findings demonstrate that backbone chemistry can be tuned as a design lever to promote nanophase separation and enhance ion transport without excessive water uptake.

Anions↗
DOE OSTI2020

All-atom molecular dynamics simulations of weak polyionic brushes: influence of charge density on the properties of polyelectrolyte chains, brush-supported counterions, and water molecules

All atom molecular dynamics (MD) simulations of planar Na+-counterion-neutralized polyacrylic acid (PAA) brushes are performed for varying degrees of ionization (and thereby varying charge density) and varying grafting density. Variation in the PE charge density (or degree of ionization) and grafting density leads to massive changes of the properties of the PE molecules (quantified by the changes in the height and the mobility of the PE brushes) as well as the local arrangement and distribution of the brush-supported counterions and water molecules within the brushes. The effect on the counterions is manifested by the corresponding variation of the counterion mobility, counterion concentration, extent of counterion binding to the charged site of the PE brushes, water-in-salt-like structure formation, and counterion-water–oxygen radial distribution function within the PE brushes. On the other hand, the effect on water molecules is manifested by the corresponding variation of water–oxygen–water–oxygen RDF, local water density, water–water and water–PE functional group hydrogen bond networks, static dielectric constant of water molecules, orientational tetrahedral order parameter, and water mobility. Enforcing such varying degree of ionization of weak polyelectrolytes is possible by changing the pH of the surrounding medium. Thus, our results provide insights into the changes in microstructure (at the atomistic level) of weak polyionic brushes at varying pH. Finally, we anticipate that this knowledge will prove to be vital for the efficient design of several nano-scale systems employing PE brushes such as nanomechanical gates, current rectifiers, etc.

42 ENGINEERING↗
DOE OSTI2022

Conjugated polyelectrolyte-based ternary exciton funnels via liposome scaffolds

There is great interest in developing inexpensive, molecular light-harvesting systems capable of efficiently converting photon energy to chemical potential energy. It is highly desirable to do so using self-assembly and in a manner that supports environmentally benign processing. A critical consideration in any such assembly is the ability to absorb a substantial fraction of the solar emission spectrum and to be able to efficiently move excited states through the space to a functional interface. We have previously shown that aqueous inter-conjugated polyelectrolyte (CPE) complexes can act as ultrafast and efficient energy-transfer antennae. Here we demonstrate formation of a hierarchically assembled, aqueous system based on an inter-CPE exciton donor/acceptor network and a lipid vesicle scaffold. Using a model small-molecule organic semiconductor embedded in the vesicle membrane, we form a ternary exciton funnel that is oriented towards the membrane interior. We show that, although energy transfer is efficient, the assembly morphology depends sensitively on preparation conditions and relative ionic stoichiometry. We propose several approaches towards stabilizing such aqueous assemblies. Furthermore, this work highlights a path to formation of an aqueous, panchromatic light-harvesting system, whose functional complexity can be systematically increased with modularity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Machine learning enabled quantification of the hydrogen bonds inside the polyelectrolyte brush layer probed using all-atom molecular dynamics simulations

The configuration of densely grafted charged polyelectrolyte (PE) brushes is strongly dictated by the properties and behavior of the counterions that screen the PE brush charges and the solvent molecules (typically water) that solvate the brush molecules and these screening counterions. Only recently, efforts have been made to study the PE brushes atomistically, thereby shedding light on the properties of brush-supported ions and water molecules. However, even for such efforts, there are limitations associated with using a generic definition to estimate certain properties of water and ions inside the brush layer. For example, water–water hydrogen bonds (HBs) will behave differently for locations outside and inside the brush layer, given the fact that the densely closely grafted PE brush molecules create a soft nanoconfinement where the water connectivity becomes highly disrupted: therefore, using the same definition to quantify the HBs inside and outside the brush layer will be unwise. In this paper, we address this limitation by employing an unsupervised machine learning (ML) approach to predict the water–water hydrogen bonding inside a cationic PE brush layer modeled using all-atom molecular dynamics (MD) simulations. Here, the ML method, which relies on a clustering approach and uses the equilibrium coordinates of the water molecules (obtained from the all-atom MD simulations) as the input, is capable of identifying the structural modification of water–water HBs (revealed through appropriate clustering of the data) inside the PE brush layer induced soft nanoconfinement. Such capabilities would not have been possible by using a generic definition of the HBs. Our calculations lead to four key findings: (1) the clusters formed inside and outside the brush layer are structurally similar; (2) the margin of the cluster is shorter inside the PE brush layer confirming the possible disruption of the HBs inside the PE brush layer; (3) the average “hydrogen–acceptor-oxygen–donor-oxygen” angle that defines the HB is reduced for the HBs formed inside the brush layer; (4) the use of the generic definition (definition usable for characterizing the HBs in brush-free bulk) leads to an overprediction of the number of HBs formed inside the PE brush layer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Stretching of immersed polyelectrolyte brushes in shear flow

In this article, the way that polymer brushes respond to shear flow has important implications in various applications, including antifouling, corrosion protection, and stimuli-responsive materials. However, there is still much to learn about the behaviours and mechanisms that govern these responses. To address this gap in knowledge, our study uses in situ X-ray reflectivity to investigate how poly(styrene sulfonate) (PSS) brushes stretch and change in different environments, such as isopropanol (a poor solvent), water (a good solvent), and aqueous solutions containing various cations (Cs + , Ba 2+ , La 3+ , and Y 3+ ). We have designed a custom apparatus that exposes the PSS brushes to both tangential shear forces from the primary flow and upward drag forces from a secondary flow. Our experimental findings clearly show that shear forces have a significant impact on how the chains in PSS brushes are arranged. At low shear rates, the tangential shear force causes the chains to tilt, leading to brush contraction. In contrast, higher shear rates generate an upward shear force that stretches and expands the chains. By analysing electron density profiles obtained from X-ray reflectivity, we gain valuable insights into how the PSS brushes respond structurally, especially the role of the diffuse layer in this dynamic behaviour. Our results highlight the importance of the initial chain configuration, which is influenced by the solvent and cations present, in shaping how polymer brushes respond to shear flow. The strength of the salt bridge network also plays a crucial role in determining how easily the brushes can stretch, with stronger networks offering more resistance to stretching. Ultimately, our study aims to enhance our understanding of polymer physics at interfaces, with a particular focus on practical applications involving polymer brushes.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Mechanically Reinforced Pseudosolid Polyelectrolyte Membranes via Layer-by-Layer Assembly for High-Performing Lithium-Metal Batteries

Ionogels are emerging as high-potential pseudosolid electrolytes for lithium-metal batteries (LMBs), leveraging their intrinsic high ionic conductivity from entrapped ionic liquid (IL) electrolytes. However, their practical application is hindered by poor mechanical strength stemming from the confinement of ILs within a polymer matrix. To address this challenge, the formation of conformal polyion coatings with functional groups is reported to be relevant to LMBs’ application on ionogels, utilizing a layer-by-layer (LbL) assembly strategy. Here, this approach significantly enhances the mechanical strength (Young's modulus and tensile strength) and electrochemical performance of ionogels, owing to the tailored interface modifications introduced by functional groups’ specific conformal polyion coatings. The core of this methodology leverages the inherent ionic structure of ionogels to enable facile interface modification through Coulombic interactions between polyanions and polycations. These conformally coated interface functionalized membranes show improved electrochemical performance when integrated with cathode materials such as LiFePO 4 (LFP) and LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) in an LMB configuration, underscoring their potential for robust, high-conductivity, pseudosolid membranes for LMB applications. These innovative pseudosolid membranes offer improved mechanical and electrochemical properties, leading to higher battery efficiency and safety, making them promising candidates for next-generation LMB technology.

25 ENERGY STORAGE↗